CN104024483B - Electrolytic Copper Foil, And Negative Electrode Collector For Secondary Battery - Google Patents
Electrolytic Copper Foil, And Negative Electrode Collector For Secondary Battery Download PDFInfo
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- CN104024483B CN104024483B CN201380003658.1A CN201380003658A CN104024483B CN 104024483 B CN104024483 B CN 104024483B CN 201380003658 A CN201380003658 A CN 201380003658A CN 104024483 B CN104024483 B CN 104024483B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Provided is an electrolytic copper foil exhibiting a high normal tensile strength, and a small tensile strength-reduction after a thermal history. The electrolytic copper foil has a normal tensile strength in the range of 500-750MPa, and a tensile strength after heating for 1 hour at 400 DEG C of at least 350MPa.
Description
Technical field
The present invention relates to a kind of electrolytic copper foil, particularly to the secondary battery cathode current collection with electrolytic copper foil as material
Body.
Background technology
Lithium ion battery has the feature that energy density is high, can obtain higher voltage, is used for notebook personal
The miniaturized electronics purposes such as computer, video camera, digital camera, portable phone.As electric automobile or general family point
The power supply of the such main equipment of scattered layout type power supply using also having reached the practical stage.
The electrode body of lithium ion battery generally has the accumulation knot much by positive pole, dividing plate and negative pole winding or stacking
Structure.Wherein, negative pole is mainly constituted by the negative electrode collector made with Copper Foil with located at the negative electrode active material on its surface.
In recent years, the densification with lithium rechargeable battery and high capacity, the volume of negative electrode active material is stretched
Amount is also increasing, and therefore the endurance that collector requires is improved.Alloy system active substance especially with Si or Sn etc.
The volumetric expansion being caused by charging reaction and conventional carbon are in a ratio of several times to decades of times.Further, since alloy system active substance
Binding agent species need closing force, therefore there is organic series solvent of high glass transition temperature using polyimides etc..
If the high binding agent of glass transition temperature, then solidification needs high temperature, therefore it is required that endurance reduces few current collection after heating
Body.
Then, in Japanese Patent No. 3850155 (patent documentation 1), to improve the tensile strength after room temperature and heating
And for the purpose of percentage elongation, record the example of the electrolytic copper foil that impurity content is few and normality tensile strength is high in Copper Foil.In day
In this JP 2008-101267 publication (patent documentation 2) and Japanese Unexamined Patent Publication 2009-299100 publication (patent documentation 3),
In order to maintain high bending property after the heating, disclose that normality tensile strength is high, the tensile strength after thermal history reduce also few
Electrolytic copper foil example.
Prior art literature
Patent documentation
Patent documentation 1：No. 3850155 publications of Japanese Patent No.
Patent documentation 2：Japanese Unexamined Patent Publication 2008-101267 publication
Patent documentation 3：Japanese Unexamined Patent Publication 2009-299100 publication
Content of the invention
Invent problem to be solved
But, although the impurity content in described electrolytic copper foil Copper Foil in patent documentation 1 is few, normality tensile strength
Height, but there is the tensile strength after thermal history and reduce such greatly problem, require as to secondary battery cathode polar body Copper Foil
Characteristic for not abundant.Although in addition, the electrolytic copper foil normality tensile strength described in patent documentation 2 and patent documentation 3
The reduction of the initial stage tensile strength after height, 180 DEG C of heating is also few, but the tension being caused by more than 180 DEG C of high-temperature heating is strong
Degree change is not clear, and in order to improve tensile strength, increased the impurity introduction volume in Copper Foil, so that as LiB negative pole
It is the conductor resistance characteristic reduction of one of most important project for collector, be not therefore suitable in this purposes.
In view of the above problems, one of problem of the present invention is, provides anti-after a kind of normality tensile strength height, thermal history
Tensile strength reduces little electrolytic copper foil.In addition, another problem of the present invention is, provide the manufacturer of this electrolytic copper foil
Method.Additionally, another problem of the present invention is, provide the secondary battery cathode current collection with this electrolytic copper foil as material
Body.
Method for solve problem
In order to solve the above problems, the present inventor is known, by by during foliation to limiting current density when electrolyte
In gum concentration optimization, the hypertrophyization of copper particle being caused by heating and softening can be suppressed, even if also keeping little after the heating
Particle diameter.In addition know, the reduction of the tensile strength after the normality tensile strength height of thus obtained electrolytic copper foil and thermal history is few.
The one aspect of the present invention being completed based on this opinion provides a kind of electrolytic copper foil, its normality tensile strength
For 500～750MPa, the tensile strength after heating 1 hour at 400 DEG C is more than 350MPa.
Another aspect of the present invention provides a kind of electrolytic copper foil, and its normality tensile strength is 500～750MPa, 400
Tensile strength after heating 1 hour at DEG C is more than 450MPa.
The still another aspect of the present invention provides a kind of electrolytic copper foil, and its normality tensile strength is 500～750MPa,
Tensile strength after heating 1 hour at 400 DEG C is more than the 50% of normality tensile strength.
The still another aspect of the present invention provides a kind of electrolytic copper foil, and its normality tensile strength is 500～750MPa,
Tensile strength after heating 1 hour at 400 DEG C is more than the 65% of normality tensile strength.
The still another aspect of the present invention provides a kind of electrolytic copper foil, and its normality tensile strength is 500～750MPa,
A diameter of less than 0.50 μm of copper particle after heating 1 hour at 400 DEG C.
In one embodiment of the electrolytic copper foil of the present invention, percentage elongation is more than 4%.
In another embodiment of the electrolytic copper foil of the present invention, percentage elongation is more than 6%.
The still another aspect of the present invention provides a kind of manufacture method of the electrolytic copper foil of the present invention, and it includes：Using containing
There is the copper electrolyte of the glue of 6～11 mass ppm, 0.14～0.16 will be set to limiting current density ratio and be electrolysed.
The still another aspect of the present invention provides a kind of secondary battery cathode collector, and it is by the electrolytic copper foil of the present invention
Constitute.
The still another aspect of the present invention provides a kind of secondary cell, and it possesses the negative electrode collector of the present invention.
The effect of invention
Tensile strength after the normality tensile strength height of the electrolytic copper foil of the present invention, thermal history reduces little.Thus, the present invention
Electrolytic copper foil can be suitable as requiring the secondary battery cathode electrode current collector of thermostability.
Specific embodiment
One of feature of electrolytic copper foil of the present invention is that normality tensile strength is high.Specifically, the cathode copper of the present invention
In one embodiment, normality tensile strength is 500～750MPa to paper tinsel.Due to normality tensile strength high can punch process,
During joint-cutting processing advantageously, therefore preferably more than 600MPa, more preferably more than 630MPa.But, if terrifically carried
High normality tensile strength, then the trend of the reduction of the tensile strength retention after thermal history on the contrary, and elongation characteristics made
Become harmful effect, therefore preferably below 750MPa, more preferably below 700MPa.
In the present invention, so-called " normality tensile strength ", represent and carry out drawing based on IPC-TM-650 under room temperature (23 DEG C)
Stretch value during strength test.
The electrolytic copper foil of the present invention another feature is that at a temperature of so at a relatively high at 400 DEG C heating 1 hour after
Tensile strength retention high.If changing a kind of view, even if this means to carry out heating also is difficult to produce by copper particle
The ruckbildung that hypertrophyization causes, even if can also keep small particle after the heating.In the past, recorded in patent documentation 1 and 2
The prior art of the improvement of thermostability of trial 180 DEG C × 1 hour or 130 DEG C × 15 hours such low temperature sides, but according to this
Known to inventor, there is not the example of the thermostability that can realize high temperature side as in the present invention.
Specifically, the electrolytic copper foil of the present invention in one embodiment, at 400 DEG C heating 1 hour after tension
Intensity is more than 350MPa, preferably more than 400MPa.
In addition, the upper limit of the tensile strength after heating 1 hour at 400 DEG C does not need especially to specify, but for example,
Below 600MPa, for example, below 580MPa, for example, below 550MPa.
In another embodiment, the tensile strength after heating 1 hour at 400 DEG C is first to the electrolytic copper foil of the present invention
More than the 50% of phase tensile strength, preferably more than 60%.Although the upper limit does not especially set, typically less than 95%,
It is more typically less than 90%, further typically less than 85%, for example, less than 80%.
In the present invention, so-called " tensile strength after heating 1 hour at 400 DEG C ", represent and heat 1 hour at 400 DEG C
Afterwards, carry out the value during tensile strength test based on IPC-TM-650 after naturally cooling to room temperature (23 DEG C).
The copper particle in addition, electrolytic copper foil of the present invention is in yet another implementation, after heating 1 hour at 400 DEG C
A diameter of less than 0.50 μm of son, preferably less than 0.45 μm, more preferably less than 0.30 μm.In addition, heating 1 is little at 400 DEG C
When after the lower limit of copper particle diameter do not need especially to specify, but be more than 0.01 μm in one embodiment, another
It is more than 0.05 μm in individual embodiment, in yet another implementation, be more than 0.07 μm.
In the present invention, so-called " the copper particle diameter after heating 1 hour at 400 DEG C ", refer to that heating 1 is little at 400 DEG C
Shi Hou, naturally cool to value after room temperature (23 DEG C), measuring using the process of chopping according to FIB-SIM cross sectional photograph.
The electrolytic copper foil of the present invention another feature is that tensile strength is high and has to a certain degree above percentage elongation.
There is the relation of inversely related in intensity and percentage elongation, the high then percentage elongation of usual intensity manifests low.By making tensile strength
High and have to a certain degree above percentage elongation, the big volume along with active substance not only can become when absorbing discharge and recharge
Change the big stress aspect being applied on paper tinsel and given play to favourable effect, but also can embody by the fortune paper tinsel in manufacturing process
Improve the beneficial effects such as the productivity ratio increase bringing.
Although percentage elongation is different according to the difference of the thickness of electrolytic copper foil, but if be thickness be 6～20 μm about
Electrolytic copper foil, then percentage elongation is more than 4%, typically more than 6%, is more typically 6～10%, for example can obtain 6～
9% big percentage elongation.So-called while there is high intensity and high-fire resistance extensibility also excellent, refer to as secondary electricity
In the case of the negative electrode collector electrolytic copper foil of pond, when absorbing discharge and recharge, the big change in volume along with active substance applies
Big stress aspect on paper tinsel plays favourable effect.In the present invention, so-called " percentage elongation ", refer to enter under room temperature (23 DEG C)
During the tensile strength test based on IPC-TM-650 for the row, test film fracture when percentage elongation.
Percentage elongation (%)=(L-Lo)/Lo × 100
Lo：Specimen length L before test：Specimen length deflection during fracture.
For the thickness of electrolytic copper foil, not restricted below, but as secondary battery cathode electrode current collector electricity consumption solution copper
In the case of paper tinsel, if being for example set to less than 20 μm, being preferably set to less than 18 μm, be more preferably set to less than 15 μm, can fill
Ground is divided to obtain above-mentioned characteristic.For the lower limit of thickness, also do not limit below, but for example, more than 6 μm.
In the case of the electrolytic copper foil manufacturing the present invention, preferably pass through, in electrolysis bath, to add and be added with 6～11 mass
The sulphuric acid system copper electrolyte of the glue of ppm, will be set to 0.14～0.16 to limiting current density ratio and to carry out to negative electrode electro-deposition.
It is, for example possible to use following electrolytic copper foil manufacture device is manufacturing：In a cell, it is configured with a diameter of about 3000mm, width
Be about the titanium system of 2500mm or stainless steel rotating cathode cylinder and separate around cylinder 3～10mm about interpolar
The electrode of distance configuration.Typically, sulphuric acid system copper electrolyte can be set to copper concentration：80～110g/L, sulfuric acid concentration：70～
110g/L.
If concentration of pectin is more than 11 mass ppm, then percentage elongation has the trend of reduction, on the other hand, if less than 6 mass
Ppm, then heat after tensile strength step-down, therefore with 6～11 mass ppm be optimal.
If to limiting current density ratio more than 0.16, heating after tensile strength step-down, on the other hand, if less than
0.14, then initial stage tensile strength step-down, therefore preferably 0.14～0.16.In the present invention, under limiting current density Billy is used
Formula calculates.
To limiting current density than=actual electric current density/limiting current density
Although limiting current density with copper concentration, sulfuric acid concentration, liquid supply speed, anode-cathode distance, electrolyte temperature and become
Change, but in our current research, normal plating (copper is with the state of samdwich) (is burnt plating, copper is with lenticular (ball with roughening plating
Shape, needle-like or rime shape etc.) state that separates out, have concavo-convex.) the electric current density of boundary be defined as limiting current density, will
The electric current density of the limit (at once will become before burning plating) of normal plating is reached in hull trough test (hull cell test)
(visually judging) is set to limiting current density.
Specifically, in hull trough test, copper concentration, sulfuric acid concentration, electrolyte temperature are set as the manufacture of Copper Foil
Condition, carries out hull trough test.Additionally, investigating this electrolyte composition, the layers of copper under electrolyte temperature forms state (copper is with stratiform
Separate out or formed with lenticular).Hereafter, the electric current density catalog based on Yamamoto Gold Plating Tester Co., Ltd., according to
There is the position of normal plating and the test block at the position of boundary of roughening plating in test block, obtain the electricity at the position of this boundary
Current density.Then, the electric current density at position this being had a common boundary is defined as limiting current density.It follows that this electrolyte group
Limiting current density under one-tenth, electrolyte temperature.In general, if anode-cathode distance is short, limiting current density has and uprises
Trend.In embodiment, used in hull trough test, test block employs the thin-film electro of Yamamoto Gold Plating Tester Co., Ltd.
Horizontal copper coin is used in pond test.
In addition, in the past in order that the shape of Copper Foil particle is neat, more than 0.17 will be set to make to limiting current density ratio
Making electrolytic copper foil is convention.The method of hull trough test is for example recorded in《め っ I this (plating practice reader)》Ball mountain
Page 157 of 30 days Qing Zhu Nikkan Kogyo Shimbun June nineteen eighty-three in page 160.
The surface of preferred pair electrolytic copper foil or the back side, more preferably antirust treatment is carried out to two sides.Antirust treatment does not limit,
But the epithelium that can enumerate independent chromated oxide is processed or chromated oxide is processed with the mixture epithelium of zinc/zinc oxide.So-called
Chromated oxide refers to following process with the mixture epithelium process of zinc/zinc oxide：Using containing zinc salt or zinc oxide and chromium
The electroplate liquid of hydrochlorate, covers the antirust coat of the zinc-chromio mixture being formed by zinc or zinc oxide and chromated oxide using plating.
As electroplate liquid, typically using K2Cr2O7、Na2Cr2O7Deng bichromate or CrO3Deng at least one and hydrogen
Alkali oxide and the mixed aqueous solution of acid.Alternatively, it is also possible to using above-mentioned aqueous solution and water-soluble zinc salt, such as ZnO,
ZnSO4·7H2At least one mixed aqueous solution such as O.
Roughening treatment can be implemented as needed before antirust treatment.As roughening particle, can be formed copper, cobalt, in nickel
1 kind of plating or their alloy plated of more than two kinds.Generally form roughening using copper, cobalt, this alloy plated of nickel
Particle.Additionally, secondary battery cathode collector Copper Foil is in order to improve thermostability and weatherability (corrosion-resistant) property, preferably in table
On the roughening treatment face on back of the body two sides, formed and be selected from cobalt-nickel alloy coating, zinc-nickel alloy coating, copper-zinc alloy coating, chromium
The antirust treatment layer of one or more of silicate layer or refractory layer and/or silane coupling layer.Alternatively, it is also possible to not form roughening grain
Son, and formed selected from one of cobalt-nickel alloy coating, zinc-nickel alloy coating, copper-zinc alloy coating, chromate coating with
On antirust treatment layer or refractory layer and/or silane coupling layer.
Can also as needed, to improve Copper Foil with the bonding force of active substance as main purpose, to two on antirust coat
Face or the silane treatment separating out face enforcement silane-coating coupling agent.As silane coupler used in this silane treatment, permissible
Enumerate olefin-based silane, epoxy silane, acrylic silane, amino system silane, sulfydryl system silane, but can properly select
Using them.Coating process can be made by the spraying of silane coupler solution spraying, using the coating of coating machine, dipping,
Any one in cast etc..
(composition of battery)
The electrolytic copper foil of the present invention can be suitable as secondary battery cathode electrode current collector.In general secondary cell has use
In by the dividing plate of negative pole, positive pole, positive pole and negative insulation and non-aqueous or water system electrolyte, form them and housed by battery case
Construction.In addition, not needing dividing plate in the case that electrolyte is for polymer dielectric.
(negative pole)
Negative pole typically by the present invention negative electrode collector and be formed at negative electrode collector one or both sides contain negative pole
The layer of active substance is constituted.As negative electrode active material, can enumerate can carry out lithium inhale the Carbonaceous matter of storage release, metal,
Metallic compound (metal-oxide, metal sulfide, metal nitride), lithium alloy etc..
As described Carbonaceous matter, graphite, coke, carbon fiber, Spherical Carbon, thermal decomposition gas phase Carbonaceous matter, resin can be enumerated
The graphite material such as sintered body or carbonaceous material；By to heat-curing resin, isotropic pitch, mesophase pitch system carbon,
The graphite material obtained from implement heat treatment at 500～3000 DEG C such as mesophase pitch based carbon fiber, mesophasespherule
Or carbonaceous material etc..
As described metal, lithium, aluminum, magnesium, stannum, silicon etc. can be enumerated.
As described metal-oxide, tin-oxide, Si oxide, Li-Ti oxide, niobium oxide, tungsten oxygen can be enumerated
Compound etc..As described metal sulfide, tin sulfide, titanium sulfide etc. can be enumerated.As described metal nitride, permissible
Enumerate lithium cobalt nitride, lithium iron-nitride, lithium manganese nitride etc..
As lithium alloy, lithium-aluminium alloy, lithium-tin alloy, Li-Pb alloy, Li-Si alloy etc. can be enumerated.
Normality tensile strength is high as described above for the electrolytic copper foil of the present invention, and the tensile strength reduction after thermal history is little,
Therefore particularly will employ the alloy system activity that volumetric expansion is big, need Si or Sn of high temperature etc. in the solidification of binding agent
Material is as particularly advantageous in the case of negative electrode active material.
Binding agent or mobility regulator (typically thickening agent) can be contained in the layer containing negative electrode active material
Deng additive.For example can add from Kynoar (PVDF), politef (PTFE), Kynoar-hexafluoropropene
The fluorine-containing polymer such as copolymer (PVDF-HFP)；Styrene butadiene ribber (SBR), acrylic rubber are (for example with (first
Base) constitute the rubber of monomer based on acrylate), fluorine system rubber (such as vinylidene fluoride rubber, tetrafluoroethylene-propylene copolymerization
Thing rubber), polybutadiene, the rubber-like such as ethylene-propylene-diene copolymer (EPDM) and sulfonated epdm；Acrylic resin
(for example based on (methyl) acrylate, being constituted resin, polyacrylic acid of monomer etc.)；Carboxymethyl cellulose (CMC), diacetyl
The cellulose-based polymer such as cellulose, hydroxypropyl cellulose；Polyvinyl alcohol；The polyalkylene oxides such as poly(ethylene oxide)；Polyimides
Etc. one or more the polymeric material suitably selecting in various polymer.Wherein, preferably comprise the mixed of CMC and SBR
Compound.By using this mixture, the adaptation of negative electrode active material and collector can be improved further.
In the layer containing negative electrode active material, conductive agent can be contained.As conductive agent, acetylene black, powder can be enumerated
The graphite-likes such as last shape expanded graphite, carbon fiber powder mince, graphitized carbon fibre ground product etc..
(positive pole)
Positive pole contains positive-active typically by positive electrode collector and the one or both sides being formed at described positive electrode collector
The layer of material is constituted.
As positive electrode collector, aluminium sheet, al mesh material etc. can be enumerated.
Layer containing positive active material for example contains active substance and binding agent.As positive active material, Ke Yiju
Go out manganese dioxide, molybdenum bisuphide, LiCoO2、LiNiO2、LiMn2O4Deng chalcogen compound.These chalcogen compounds can also be with 2
Plant above mixture to use.Particularly, use lithium-transition metal composite oxide in lithium rechargeable battery more.
In the layer containing positive active material, in the same manner as the layer containing negative electrode active material can contain binding agent or
The additives such as mobility regulator (typically thickening agent).The example of narration in the concrete such as layer containing negative electrode active material
Son.
In the layer containing active substance, the graphite-like such as acetylene black, powder expanded graphite, carbon fibre can be contained further
Dimension ground product, graphitized carbon fibre ground product etc. are as conductive aid.
(dividing plate)
Between positive pole and negative pole, dividing plate can be configured.As dividing plate, for example can be using the thickness with 20～30 μm
Polyethylene porous membrane, polypropylene porous film etc..The polymer dielectrics such as solid or gel is being used as nonaqueous electrolyte
In the case of it is also possible to omit dividing plate.
(nonaqueous electrolyte)
Nonaqueous electrolyte can be using the non-aqueous solution electrolysis containing nonaqueous solvent and the electrolyte being dissolved in this nonaqueous solvent
The form of liquid.
As nonaqueous solvent, can enumerate ethylene carbonate, dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate, γ-
Butyrolactone, methyl propionate etc..The species of nonaqueous solvent used can be one kind or two or more.
As electrolyte, lithium perchlorate (LiClO can be enumerated4), lithium lithium phosphate (LiPF6), tetrafluoride Lithium biborate
(LiBF4), lithium arsenic acid lithium (LiAsF6) etc..Electrolyte both can be used alone it is also possible to be used with the form of mixture.
In addition, nonaqueous electrolyte can also adopt the form of the polymer dielectric such as solid or gel.
[embodiment]
Embodiments of the invention given below, but it is not intended to limit the invention to below example.
In a cell, configure a diameter of about 3133mm, the width rotary drum of titanium for 2476.5mm and in cylinder
Surrounding separate 5mm about anode-cathode distance configuration electrode.To in this electrolysis bath, importing is added with the concentration described in table 1
The copper sulfate solution of glue.Hereafter, be adjusted to described in table 1 to limiting current density ratio, so that copper is separated out in rotary drum
Surface, peels the copper separating out the surface in rotary drum off, is continuously manufactured by out example and the ratio with the thickness described in table 1
Electrolytic copper foil compared with example.
To obtained each electrolytic copper foil, condition determination as described above, have rated normality tensile strength, 400
At DEG C heating 1 hour after tensile strength, at 400 DEG C heating 1 hour after tensile strength with respect to normality tensile strength
Than (conservation rate), percentage elongation, at 400 DEG C heating 1 hour after copper particle diameter.The results are shown in Table 1.
[table 1]
Claims (10)
1. a kind of electrolytic copper foil, its normality tensile strength is 500～750MPa, the tensile strength after heating 1 hour at 400 DEG C
For more than 350MPa, a diameter of less than 0.50 μm of copper particle after heating 1 hour at 400 DEG C.
2. a kind of electrolytic copper foil, its normality tensile strength is 500～750MPa, the tensile strength after heating 1 hour at 400 DEG C
For more than 450MPa.
3. a kind of electrolytic copper foil, its normality tensile strength is 500～750MPa, the tensile strength after heating 1 hour at 400 DEG C
A diameter of less than 0.50 μm of the copper particle for more than the 50% of normality tensile strength, after heating 1 hour at 400 DEG C.
4. a kind of electrolytic copper foil, its normality tensile strength is 500～750MPa, the tensile strength after heating 1 hour at 400 DEG C
A diameter of less than 0.50 μm of the copper particle for more than the 65% of normality tensile strength, after heating 1 hour at 400 DEG C.
5. a kind of electrolytic copper foil, its normality tensile strength is 500～750MPa, and the copper particle after heating 1 hour at 400 DEG C is straight
Footpath is less than 0.50 μm.
6. the electrolytic copper foil according to any one of Claims 1 to 5, its percentage elongation is more than 4%.
7. the electrolytic copper foil according to any one of Claims 1 to 5, its percentage elongation is more than 6%.
8. the manufacture method of the electrolytic copper foil any one of a kind of claim 1～7, it includes：Using containing 6～11 matter
The copper electrolyte of the glue of amount ppm, actual electric current density/limiting current density is set to 0.14～0.16 and is electrolysed.
9. a kind of secondary battery cathode collector, it is made up of the electrolytic copper foil any one of claim 1～7.
10. a kind of secondary cell, it possesses the negative electrode collector described in claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012047397A JP5722813B2 (en) | 2012-03-02 | 2012-03-02 | Electrode copper foil and negative electrode current collector for secondary battery |
| JP2012-047397 | 2012-03-02 | ||
| PCT/JP2013/055734 WO2013129664A1 (en) | 2012-03-02 | 2013-03-01 | Electrolytic copper foil, and negative electrode collector for secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104024483A CN104024483A (en) | 2014-09-03 |
| CN104024483B true CN104024483B (en) | 2017-02-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380003658.1A Active CN104024483B (en) | 2012-03-02 | 2013-03-01 | Electrolytic Copper Foil, And Negative Electrode Collector For Secondary Battery |
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| Country | Link |
|---|---|
| US (2) | US20140346048A1 (en) |
| EP (1) | EP2821527B1 (en) |
| JP (1) | JP5722813B2 (en) |
| KR (2) | KR20140063854A (en) |
| CN (1) | CN104024483B (en) |
| MY (1) | MY173639A (en) |
| PH (1) | PH12014501201B1 (en) |
| TW (1) | TWI516642B (en) |
| WO (1) | WO2013129664A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI553946B (en) * | 2014-01-08 | 2016-10-11 | 金居開發銅箔股份有限公司 | Heat-resistant copper foil for lithium battery and manufacturing method thereof |
| KR101500565B1 (en) * | 2014-03-20 | 2015-03-12 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, current collector, anode and lithium battery comprising foil |
| KR101500566B1 (en) * | 2014-03-20 | 2015-03-12 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, current collector, anode and lithium battery comprising foil |
| JP2015198020A (en) * | 2014-04-01 | 2015-11-09 | 古河電気工業株式会社 | Surface treatment copper foil for negative electrode, negative electrode and lithium ion secondary battery using the same |
| CN105336883A (en) * | 2015-10-19 | 2016-02-17 | 宁德新能源科技有限公司 | Lithium ion battery flexible packaging material, and lithium ion battery prepared from lithium ion battery flexible packaging material |
| WO2017217085A1 (en) * | 2016-06-14 | 2017-12-21 | 古河電気工業株式会社 | Electrolytic copper foil, lithium ion secondary cell negative electrode, lithium ion secondary cell, and printed wiring board |
| TWI658506B (en) | 2016-07-13 | 2019-05-01 | 美商英奧創公司 | Electrochemical methods, devices and compositions |
| KR20180040754A (en) | 2016-10-12 | 2018-04-23 | 케이씨에프테크놀로지스 주식회사 | Easily Handleable Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| KR101734840B1 (en) * | 2016-11-11 | 2017-05-15 | 일진머티리얼즈 주식회사 | Electrolytic copper foil of secondary battery enhanced for flexibility resistance and manufacturing method thereof |
| KR101733408B1 (en) * | 2016-11-11 | 2017-05-10 | 일진머티리얼즈 주식회사 | Electrolytic Copper Foil for secondary battery and manufacturing method thereof |
| KR101951637B1 (en) * | 2017-04-07 | 2019-02-26 | 일진머티리얼즈 주식회사 | Negative electrode for secondary battery, method thereof and lithium secondary batteries fabricated by using the same |
| KR102433032B1 (en) * | 2017-07-31 | 2022-08-16 | 에스케이넥실리스 주식회사 | Copper foil free from generation of wrinkle, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| US10205170B1 (en) * | 2017-12-04 | 2019-02-12 | Chang Chun Petrochemical Co., Ltd. | Copper foil for current collector of lithium secondary battery |
| EP3547424B1 (en) * | 2018-03-29 | 2024-06-05 | Toyota Jidosha Kabushiki Kaisha | Anode, and sulfide solid-state battery |
| JP2019175838A (en) * | 2018-03-29 | 2019-10-10 | トヨタ自動車株式会社 | Anode, and sulfide solid-state battery |
| WO2020059187A1 (en) * | 2018-09-19 | 2020-03-26 | Kabushiki Kaisha Toshiba | Electrode, secondary battery, battery pack, vehicle, and stationary power supply |
| JP7098558B2 (en) * | 2018-09-19 | 2022-07-11 | 株式会社東芝 | Electrodes, rechargeable batteries, battery packs, vehicles, and stationary power supplies |
| JP7127631B2 (en) * | 2019-10-21 | 2022-08-30 | トヨタ自動車株式会社 | Method for manufacturing positive electrode active material, and method for manufacturing lithium ion battery |
| KR20210109971A (en) * | 2020-02-28 | 2021-09-07 | 현대자동차주식회사 | Manufacturing method of negative electrode for lithium ion battery and lithium ion battery including negative electrode manufactured by the method |
| CN111455414A (en) * | 2020-03-09 | 2020-07-28 | 深圳市惟华电子科技有限公司 | Additive for producing gradual change type electrolytic copper foil |
| CN111607810A (en) * | 2020-07-14 | 2020-09-01 | 安徽铜冠铜箔集团股份有限公司 | Efficient production method of ultrathin electrolytic copper foil |
| WO2023057067A1 (en) * | 2021-10-07 | 2023-04-13 | Circuit Foil Luxembourg | Copper foil with high engery at break and secondary battery comprising the same |
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| CN1105398A (en) * | 1993-10-22 | 1995-07-19 | 古尔德电子有限公司 | Electrodeposited copper foil and process for making same |
| JP2008285727A (en) * | 2007-05-18 | 2008-11-27 | Furukawa Circuit Foil Kk | Electrolytic copper foil with high tensile-strength, and manufacturing method therefor |
| CN103221583A (en) * | 2010-11-22 | 2013-07-24 | 三井金属矿业株式会社 | Surface treated copper foil |
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| JP5074611B2 (en) * | 2011-03-30 | 2012-11-14 | Ｊｘ日鉱日石金属株式会社 | Electrolytic copper foil for secondary battery negative electrode current collector and method for producing the same |
| JP5148726B2 (en) * | 2011-03-30 | 2013-02-20 | Ｊｘ日鉱日石金属株式会社 | Electrolytic copper foil and method for producing electrolytic copper foil |
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2012
- 2012-03-02 JP JP2012047397A patent/JP5722813B2/en active Active
-
2013
- 2013-03-01 EP EP13754147.0A patent/EP2821527B1/en active Active
- 2013-03-01 US US14/359,826 patent/US20140346048A1/en not_active Abandoned
- 2013-03-01 TW TW102107222A patent/TWI516642B/en active
- 2013-03-01 WO PCT/JP2013/055734 patent/WO2013129664A1/en active Application Filing
- 2013-03-01 KR KR1020147010529A patent/KR20140063854A/en active Application Filing
- 2013-03-01 MY MYPI2014701482A patent/MY173639A/en unknown
- 2013-03-01 KR KR1020177002203A patent/KR20170012604A/en not_active Application Discontinuation
- 2013-03-01 CN CN201380003658.1A patent/CN104024483B/en active Active
-
2014
- 2014-05-28 PH PH12014501201A patent/PH12014501201B1/en unknown
-
2019
- 2019-10-02 US US16/590,730 patent/US20200036010A1/en not_active Abandoned
Patent Citations (3)
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| CN1105398A (en) * | 1993-10-22 | 1995-07-19 | 古尔德电子有限公司 | Electrodeposited copper foil and process for making same |
| JP2008285727A (en) * | 2007-05-18 | 2008-11-27 | Furukawa Circuit Foil Kk | Electrolytic copper foil with high tensile-strength, and manufacturing method therefor |
| CN103221583A (en) * | 2010-11-22 | 2013-07-24 | 三井金属矿业株式会社 | Surface treated copper foil |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013181236A (en) | 2013-09-12 |
| EP2821527A1 (en) | 2015-01-07 |
| EP2821527B1 (en) | 2018-05-02 |
| TW201343974A (en) | 2013-11-01 |
| MY173639A (en) | 2020-02-12 |
| WO2013129664A1 (en) | 2013-09-06 |
| EP2821527A4 (en) | 2015-10-28 |
| PH12014501201A1 (en) | 2014-09-08 |
| KR20170012604A (en) | 2017-02-02 |
| US20140346048A1 (en) | 2014-11-27 |
| CN104024483A (en) | 2014-09-03 |
| KR20140063854A (en) | 2014-05-27 |
| TWI516642B (en) | 2016-01-11 |
| US20200036010A1 (en) | 2020-01-30 |
| JP5722813B2 (en) | 2015-05-27 |
| PH12014501201B1 (en) | 2014-09-08 |
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